Method of fabricating iridium-based materials and structures on substrates, and iridium source reagents therefor

ABSTRACT

A method of forming an iridium-containing film on a substrate, from an iridium-containing precursor thereof which is decomposable to deposit iridium on the substrate, by decomposing the precursor and depositing iridium on the substrate in an oxidizing ambient environment which may for example contain an oxidizing gas such as oxygen, ozone, air, and nitrogen oxide. Useful precursors include Lewis base stabilized Ir(I)β-diketonates and Lewis base stabilized Ir(I) β-ketoiminates. The iridium deposited on the substrate may then be etched for patterning an electrode, followed by depositing on the electrode a dielectric or ferroelectric material, for fabrication of thin film capacitor semiconductor devices such as DRAMs, FRAMs, hybrid systems, smart cards and communication systems.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to a method of forming iridium- oriridium-containing materials on substrates, such as Ir-based electrodestructures for microelectronic devices and subassemblies, as well as toIr source reagent materials, and novel dielectric capacitor orferroelectric material device structures.

[0003] 2. Description of the Related Art

[0004] Iridium (Ir) and iridium oxide (IrO₂) are of great interest foruse as electrode materials in both dynamic random access memories(DRAMs) and for ferroelectric-based memory devices (FRAMs) whichincorporate perovskite metal oxide thin-films as the capacitor layer.

[0005] The advantages of Ir over other possible electrode materialsinclude ease of deposition, the ability to “dry etch” the material, theability to form a stable conducting oxide at high temperatures in anoxidizing environment, and the ability to operate reliably at hightemperatures in a working device.

[0006] The deposition and processing of Ir-based electrodes is highlydesirable in view of the aforementioned advantages. Further, theformation of IrO₂ acts as a diffusion barrier to oxidation of conductingpolysilicon vias or plugs, as is required in high density DRAM or FRAMdevices.

[0007] Based on the need for Ir-based electrodes, the art has continuedto seek improvements in source materials and deposition techniques forthe formation of Ir-based films.

[0008] The art has variously disclosed the chemical vapor deposition ofiridium for the manufacture of electronic devices in a reducingatmosphere, such as hydrogen gas environment. The art has taught the useof such reducing atmosphere for the purpose of achieving the depositionof element metal iridium for electrodes in applications in which hightemperature dielectric materials (e.g., SBT, BST, PZT, PLZT, PNZT,LaCaMnO₃, etc., wherein SBT strontium bismuth tantalate, BST=bariumstrontium titanate, PZT=lead zironium titanate, PLZT=lead lanthanumzirconium titanate, PNZT=lead niobium zirconium titanate) are depositedon the electrode, to minimize the possibility of degradation of thedielectric in such applications and to concurrently achieve theformation of high purity metal.

[0009] The art has especially sought improvements in process technologyfor the formation of semiconductor and ferroelectric structures thatemploy Ir electrodes specifically associated with complex dielectric orferroelectric material layers as thin-film capacitors.

[0010] It is an object of the present invention to provide novel sourcereagents and a process for the formation of iridium-based electrodesthat achieve a material simplification in fabrication efficiency andcost, and provide an electrode structure that is highly advantageous forintegration with silicon device technology, being efficient, oxygenreactive, oxygen impermeable, and readily fabricated.

[0011] It is another object of the invention to provide a simplifiedmethod for the fabrication of metal oxide thin film capacitor structuresincluding iridium, iridium oxide or iridium-containing electrodeelements, as metal contacts for the oxide DRAM and FRAM devices.

[0012] Other objects and advantages of the present invention will bemore fully apparent from the ensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

[0013] This invention relates to a method of forming iridium- oriridium-containing materials on substrates, such as Ir-based electrodestructures for microelectronic devices and subassemblies, and catalyticmaterials, as well as to Ir source reagent materials, and noveldielectric material structures.

[0014] As used herein, the term “Ir-based” or “iridium-based” refersbroadly to elemental iridium, iridium oxide, iridium-containing materialcompositions and combinations thereof.

[0015] The present invention also relates to novel high temperaturedielectric or ferroelectric thin film capacitor structures includingIr-based electrode elements.

[0016] In one aspect, the invention relates to a method of forming aniridium-containing film on a substrate, from an iridium-containingprecursor thereof that is decomposed to deposit iridium on thesubstrate, such method comprising decomposing the precursor anddepositing iridium on the substrate in an oxidizing ambient environment.The deposition of iridium on the substrate may be carried out in anysuitable manner and by any appropriate techniques of the art, includingchemical vapor deposition (CVD), assisted CVD, or physical depositionmethods such as ion plating, rapid thermal processing, molecular beamepitaxy, etc.

[0017] As used herein, the term “oxidizing ambient environment” means anenvironment including oxygen-containing gas, such as oxygen, ozone, air,nitrogen oxide (NO_(x)), or the like. Such oxidizing atmosphere may beprovided in a deposition chamber or reaction vessel in which thedeposition is carried out, and enables the formation of iridium oriridium oxide on the substrate. Accordingly, the deposition may beconducted in an ambient air environment, thereby simplifying theformation of the iridium-containing film on the substrate. In analternate embodiment, IrO₂ may be formed in a post-deposition processfrom Ir metal by treatment in an oxidizing environment.

[0018] The Ir precursor material may be of any suitable composition andtype. In preferred practice of the present invention, the precursor maysuitably comprise a Lewis base-stabilized β-diketonate iridiumcomposition or a Lewis base-stabilized beta-ketoiminate composition, ashereafter more fully described.

[0019] When the iridium-containing film is employed to form an electrodeor other patterned structure on the substrate, the deposited iridium oriridium oxide film may be dry etched with a halogen-based plasma and/orpreferably, XeF₂, as more fully described in concurrently filed U.S.patent application Ser. No. 08/966,796 filed Nov. 10, 1997 in the namesof Thomas H. Baum and Frank DiMeo, Jr., for “Method for Etch Fabricationof Iridium-Based Electrode Structures,” the disclosure of which herebyis incorporated herein in its entirety. In such dry etching of adeposited iridium or iridium oxide film, the etch rates can optionallybe enhanced through the use of Lewis-based adducts or electronback-bonding species such as carbon monoxide, trifluorophosphine,trialkylphosphines or other suitable Lewis base.

[0020] In yet another aspect of the present invention, theiridium-containing film subsequent to its formation as an electrodestructure may have deposited thereon a high temperature dielectricand/or ferroelectric material. An oxidizing ambient environment may beemployed for the deposition of the iridium-containing film or may beused solely during the deposition of the oxide dielectric/ferroelectric.

[0021] It may therefore be unnecessary to purge the chamber of areducing atmosphere, or to transfer the substrate article bearing theiridium-containing film from the iridium deposition chamber to adielectric/ferroelectric deposition chamber, as has been done in theprior art to accommodate the usage of hydrogen or other reducing gas(forming gas) atmospheres in the iridium electrode formation step.

[0022] The method of this invention therefore achieves a substantialsimplification of the procedure for forming a capacitor or othermicroelectronic device in which the iridium-containing electrode isovercoated with a dielectric or ferroelectric material.

[0023] Another aspect of the invention relates to a microelectronicdevice structure comprising an iridium oxide electrode elementovercoated by a high temperature dielectric, e.g., SBT, PZT, BST, PLZT,PNZT, LaCaMnO₃, etc., wherein the electrode is conductively operative inrelation to the high temperature dielectric. As used herein, hightemperature dielectric refers to a dielectric material deposited on theelectrode at a temperature above about 300° C. By way of example,dielectric films of lead zirconium titanate (PZT) are typicallydeposited at temperatures on the order of 500-600° C.

[0024] Yet another aspect of the invention relates to a compositioncomprising an organic solvent solution of an Ir(I) reagent, wherein theIr(I) reagent is selected from the group consisting of:

[0025] Lewis base stabilized Ir(I) B-diketonates of formula I:

[0026] wherein R and R′ may be alike or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base; and

[0027] Lewis base stabilized Ir(I) β-ketoiminates of formula II:

[0028] wherein R, R′, and R″ are the same or different, and areindependently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base; and

[0029] the organic solvent solution comprises a non-polar solvent, suchas C₅-C₁₂ hydrocarbon alkanes (e.g., hexane, heptane, octane, nonane anddecane) and C₆-C₁₀ hydrocarbon aryls (e.g., benzene, toluene andxylene).

[0030] Yet another aspect of the invention relates to a compositioncomprising a non-polar solvent solution of a cyclooctadiene (COD) adductof an Ir(I) beta-diketonate.

[0031] Other aspects, features and embodiments of the invention will bemore fully apparent from the ensuing disclosure and appended claims.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

[0032] The following patents and patent applications are herebyincorporated herein by reference in their respective entireties:

[0033] U.S. patent application Ser. No. 08/966,796 filed Nov. 10, 1997in the names of Thomas H. Baum and Frank DiMeo, Jr., for “Method forEtch Fabrication of Iridium-Based Electrode Structures;”

[0034] U.S. Pat. No. 5,840,897 issued Nov. 24, 1998 in the names ofPeter S. Kirlin, Duncan W. Brown, Thomas H. Baum, Brian A. Vaartstra andRobin A. Gardiner for “Metal Complex Source Reagents for Chemical VaporDeposition;”

[0035] U.S. patent application Ser. No. 08/484,654 filed Jun. 7, 1995 inthe names of Robin A. Gardiner, et al. for “Method of Forming MetalFilms on a Substrate by Chemical Vapor Deposition;”

[0036] U.S. Pat. No. 5,820,664 issued Oct. 13, 1998 in the names ofRobin A. Gardiner et al. for “Precursor Compositions for Chemical VaporDeposition, and Ligand Exchange Resistant Metal-Organic PrecursorSolutions Comprising Same;”

[0037] U.S. Pat. No. 5,204,314 issued Apr. 20, 1993 in the names ofPeter S. Kirlin, et al. for “Method for Delivering an Involatile Reagentin Vapor Form to a CVD Reactor;”

[0038] U.S. Pat. No. 5,453,494 issued Sep. 26, 1995 in the names ofPeter S. Kirlin, et al. for “Metal Complex Source Reagents for MOCVD;”

[0039] U.S. Pat. No. 5,916,359 issued Jun. 29, 1999 in the names ofThomas H. Baum, et al. for “Alkane and Polyamine Solvent Compositionsfor Liquid Delivery Chemical Vapor Deposition;”

[0040] U.S. Pat. No. 5,923,970 issued Jul. 13, 1999 in the names ofPeter S. Kirlin, et al. for Method of Fabricating a FerroelectricCapacitor with a Graded Barrier Layer Structure;” and

[0041] U.S. Pat. No. 5,719,417 issued Feb. 17, 1998 in the names ofJeffrey Roeder, et al. for “Ferroelectric Integrated Circuit Structure.”

[0042] As used herein, the term “Lewis base” means a compound orchemical moiety that forms a bond by donating a pair of electrons. Thecompositions of the present invention containing the Lewis baseconstituent are understood to be devoid of other components thatpreclude the electron donor character of the Lewis base constituent frombeing present.

[0043] With respect to the Ir(I) precursor compositions of theinvention, as hereinafter more fully described, it is to be appreciatedthat the compositions may be specifically characterized as comprising,consisting or consisting essentially of the constituents specificallyreferenced or described herein, and such compositions may specificallybe characterized as being free, substantially free or devoid of anyconstituents not specifically referenced or described herein, as may beclaimed hereinafter at any time during the proceedings involving theapplication hereof, or an application based hereon.

[0044] The present invention relates to the discovery that Ir-basedelectrode structures can be readily formed without the necessity ofdepositing the Ir component from a precursor or source material in areducing atmosphere, as has heretofore been the approach and objectiveof the prior art.

[0045] Contrariwise, the present invention contemplates a method offorming an iridium-containing film on a substrate, from aniridium-containing precursor thereof which is decomposed to depositiridium on the substrate, in which the decomposition of the precursorand the deposition of iridium on the substrate is carried out in anoxidizing ambient environment to deposit iridium in the form of iridiumper se or in the form of iridium oxide.

[0046] Iridium may be deposited on the substrate in the method of thepresent invention in any suitable manner, including chemical vapordeposition, liquid delivery, sputtering, ablation, or any other suitabletechnique known in the art for deposition of metal on a substrate from ametal-organic or other precursor source material. Among the foregoing,chemical vapor deposition is preferred when the iridium-based structuresbeing formed have critical dimensions below about 0.5 microns.

[0047] In the method of the invention, the precursor for the iridiumcomponent may be any suitable iridium precursor compound, complex orcomposition that is advantageous for yielding iridium for deposition onthe substrate. The iridium precursor may for example comprise a Lewisbase-stabilized P-diketonate iridium composition or a Lewisbase-stabilized β-ketoiminate composition, of the formulae:

[0048] Lewis base stabilized Ir(I) β-diketonates of formula I:

[0049] wherein R and R′ are the same or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base, preferably alkene, diene, cycloalkene,cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetricalor asymmetrical), amine, diamine, triamine, tetraamine, ether,tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine,carbonyl, dialkyl sulfide, vinyltrimethylsilane, andallyltrimethylsilane,

[0050] or

[0051] Lewis base stabilized Ir(I) β-ketoiminates of formula II:

[0052] wherein R, R′, and R″ are the same or different, and areindependently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base, preferably selected from the group consistingof alkene, diene, cycloalkene, cyclodiene, cyclooctatetraene, alkyne,substituted alkyne (symmetrical or asymmetrical), amine, diamine,triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme, triglyme,tetraglyme, phosphine, carbonyl, dialkyl sulfide, vinyltrimethylsilane,and allyltrimethylsilane.

[0053] For the Lewis base in the above precursors of formulae I and II,one or more Lewis base molecules may be preferred, especially for ether,cyclic ether, tetrahydrofuran, alkene, alkyne, carbonyl and phosphineligands. In some embodiments of precursors of formula II, R and R′ maybe identical and R″ will be independently selected from the substituentslisted above.

[0054] In CVD-based embodiments of the present invention, either abubbler or organic solution liquid delivery can be utilized for thechemical vapor deposition of the Ir/IrO₂ thin film. The specificprecursor may be suitably optimized for the delivery and transport ofthe precursor to the CVD reactor. The precursor is decomposed in thepresence of an oxidant (e.g., O_(2, O) ₃, or N₂O) to preferentiallydeposit the metal Ir (<500° C.) or the oxide, IrO₂ (>550° C.). In someapplications, the formation of a bi-layered Ir/IrO₂ film may bepreferred.

[0055] The etching of Ir and IrO₂ in the practice of the invention,after the initial formation of the iridium-containing film, may becarried out with the use of halogen-based systems, such as chlorine,bromine, and fluorine based plasma or ion beam etch chemistries. Theformation of halogens of Ir(I) and Ir(III) can be exploited to etch andpattern electrodes for semiconductor and ferroelectric deviceapplications. In systems where IrO₂ is present, the use of either areducing pre-treatment (to return the iridium oxide to Ir metal) or theuse of fluorine etchants may be preferred. The formation and removal ofetch by-products depends on the volatility of the halide species. Theaddition of stabilizing co-reactants may usefully be employed tofacilitate the removal and etching of the materials.

[0056] The iridium-containing films deposited in accordance with themethod of the present invention may be etched with a dry etch method, asmore fully described in the aforementioned co-pending U.S. patentapplication Ser. No. 08/966,796 filed Nov. 10, 1997 in the names ofThomas H. Baum and Frank DiMeo Jr. for “Method for Etch Fabrication ofIridium-Based Electrode Structures,” optionally using specific chemicalenhancements to the rate of etching. The addition of carbon monoxide,trifluorophosphine, or trialkyl phosphines can accelerate the rate ofetching by enhancing the volatility of the produced etch by-products.

[0057] For example, in the etching of the Ir-containing film on thesubstrate, the removal rate for the process may be advantageouslyaccelerated by the presence of carbon monoxide (CO). The rates arestrongly dependent upon the gas-phase partial pressure of the reactantsin elevated substrate temperature regimes (e.g., 725-975° C.). Thepresence of CO may serve to enhance the reactant volatility through theformation of (CO)_(y)IrX₃ (where X=Cl, Br) and for Ir(CI)₄. IrF₆ mayalso be employed for such purpose. These materials can be usedadvantageously for etching Ir in halogen-based plasmas, ion beams and inhybrid etching schemes.

[0058] In some instances, it may be desirable to convert the iridiumoxide material deposited on the substrate to a pure iridium metal for aspecific fabrication or device application. In such instance, thedeposited film of iridium oxide may be exposed to a reducing gas, suchas hydrogen, forming gas, CO, ROH, etc, to effect such conversion.

[0059] After its formation and any additional patterning, theiridium-containing electrode may have deposited thereon a hightemperature dielectric and/or ferroelectric material in the sameoxidizing ambient environment employed for the deposition of theiridium-containing film.

[0060] It is therefore unnecessary to purge the chamber of a reducingatmosphere, or to transfer the substrate article bearing theiridium-containing film from the iridium deposition chamber to adielectric/ferroelectric deposition chamber, as has been done in theprior art to accommodate the usage of hydrogen or other reducing gas(forming gas) atmospheres in the iridium electrode formation step. Themethod of the invention therefore achieves a substantial simplificationof the procedure for forming a capacitor or other microelectronic devicein which the iridium-containing electrode is overcoated with adielectric or ferroelectric material.

[0061] The iridium films deposited in the practice of the presentinvention may therefore be utilized for the formation of electrode andother elements of semiconductor devices, such as for example DRAMs,FRAMs, hybrid systems, smart cards and communication systems, as well asany other applications in which the thin films of iridium and/or iridiumoxide are advantageously employed, such as catalytic systems.

[0062] As a specific example of an Ir(I) precursor composition that maybe usefully employed in the broad practice of the present invention, aprecursor comprising a cycloalkenyl moiety such as the cyclooctadiene(COD) adduct of Ir(I) beta-diketonate, in a suitable hydrocarbon solvent(octane), may be employed for liquid delivery MOCVD of iridium forelectrode formation in the manufacture of semiconductor devices such asthose mentioned in the preceding paragraph.

[0063] The hydrocarbon solvents useful for such purpose may for exampleinclude non-polar solvents, e.g., C₅-C₁₂ alkane solvents such as hexane,octane, etc., C₁-C₈ alkyl-substituted benzene solvents, e.g., toluene,xylene or other hydrocarbon substituted solvents, e.g., diethylether ortetrahydrofuran, etc. The solvent medium for the cyclooctadiene (COD)adduct of Ir(I) beta-diketonate desirably does not include alkanolicsolvents (e.g., ethanol and isopropanol) since the presence of suchsolvents may lead to premature decomposition of the source reagentcomplex in solution, prior to delivery or during vaporization of theprecursor mixture.

[0064] As used herein, the term “non-polar solvent” means a hydrocarbonalkane(s) or aryl solvent having a dielectric constant (ε) of from about1 to about 15. The dielectric constant provides a measure of thesolvent's capacity to separate ionic charge, so that the higher thevalue of the dielectric constant, the more polar the solvent. Further,these solvents are characterized by being primarily hydrocarbons withoutthe presence of polar substituents, such as oxygen, sulfur, chlorine,bromine, fluorine and other polarizable groups.

[0065] The β-diketonate ligand in such cyclooctadiene (COD) adduct ofIr(I) β-diketonate may be of any suitable type, including theillustrative β-diketonate ligand species set out in Table A below: TABLEA Beta-diketonate ligand Abbreviation2,2,6,6-tetramethyl-3,5-heptanedionato thd1,1,1-trifluoro-2,4-pentanedionato tfac1,1,1,5,5,5-hexafluoro-2,4-pentanedionato hfac6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato fod2,2,7-trimethyl-3,5-octanedionato tod1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedionato dfhd1,1,1-trifluoro-6-methyl-2,4-heptanedionato tfmhd

[0066] The liquid delivery MO CVD system for growing the iridium filmsof the invention may for example comprise a system of the type disclosedin U.S. Pat. No. 5,204,314 issued Apr. 20, 1993 to Peter S. Kirlin etal. and in U.S. Pat. No. 5,536,323 issued Jul. 16, 1996 to Peter S.Kirlin et al., which utilize heated vaporization structures such asmicroporous disk elements to effect high rate vaporization of the sourcereagent materials for the metal oxide film. In operation, liquid sourcereagent compositions are flowed onto the vaporization structure forflash vaporization. Vapor thereby is produced for transport to thedeposition zone, e.g., the CVD reactor. The liquid delivery systems ofthese patents provide high efficiency generation of vapor from whichfilms may be grown on substrates.

[0067] The precursor vapor formed by the high rate vaporizationapparatus is transported to a chemical vapor deposition zone containinga substrate, e.g., a wafer provided on a heated susceptor. Uponcontacting of the precursor vapor with the wafer, the metal componentsof the vapor are deposited on the wafer surface. The vapor may bedelivered in the chemical vapor deposition chamber by a disperser suchas a showerhead or nozzle, to provide a uniform flux of the vapor acrossthe width of the wafer, to yield a correspondingly uniform thickness ofdeposited metal-containing film on the wafer. The process conditions(temperature, pressure, flow rate and composition of the vapor) may besuitably controlled to ensure an optimum process result for the specificMOCVD operation being conducted in the process system.

[0068] While the invention has been variously disclosed herein withreference to illustrative embodiments and features, it will beappreciated that the embodiments and features described hereinabove arenot intended to limit the invention, and that other variations,modifications and other embodiments will suggest themselves to those ofordinary skill in the art. The invention therefore is to be broadlyconstrued, consistent with the claims hereafter set forth.

What is claimed is:
 1. A method of forming an iridium-containing film ona substrate, from an iridium-containing precursor thereof that isdecomposable to deposit iridium on the substrate, said method comprisingdecomposing the precursor and depositing iridium on the substrate in anoxidizing ambient environment.
 2. The method according to claim 1,wherein the oxidizing ambient environment comprises an atmospherecontaining an oxidizing gas selected from the group consisting ofoxygen, ozone, air, and nitrogen oxide.
 3. The method according to claim1, wherein the iridium deposited on the substrate comprises elementaliridium.
 4. The method according to claim 1, wherein the iridiumdeposited on the substrate comprises iridium oxide, or a combination ofiridium and iridium oxide.
 5. The method according to claim 1, whereinthe precursor comprises a composition selected from the group consistingof: Lewis base stabilized Ir(I) B-diketonates of formula I:

wherein R and R′ may be alike or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base; and Lewis base stabilized Ir(I) β-ketoiminatesof formula II:

wherein R,R′, and R″ are the same or different, and are independentlyselected from the group consisting of H, aryl, perfluoroaryl, C₁-C₆alkyl, or C₁-C₆ perfluoroalkyl, and L is coordinating Lewis base.
 6. Themethod according to claim 5, wherein the coordinating Lewis base isselected from the group consisting of alkene, diene, cycloalkene,cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetricalor asymmetrical), amine, diamine, triamine, tetraamine, ether,tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine,carbonyl, dialkyl sulfide, vinyltrimethylsilane, andallyltrimethylsilane.
 7. The method according to claim 1, wherein theoxidizing ambient environment comprises air.
 8. The method according toclaim 1, wherein the decomposition of the precursor and deposition ofiridium on the substrate is carried out by a process selected from thegroup consisting of chemical vapor deposition (CVD), assisted-CVD, ionplating, rapid thermal processing, and molecular beam epitaxy.
 9. Themethod according to claim 1, wherein the precursor comprises acomposition selected from the group consisting of: Lewis base stabilizedIr(I) β-diketonates of formula I:

wherein R and R′ may be alike or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base.
 10. The method according to claim 9, whereinthe coordinating Lewis base is selected from the group consisting ofalkene, diene, cycloalkene, cyclodiene, cyclooctatetraene, alkyne,substituted alkyne (symmetrical or asymmetrical), amine, diamine,triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme, triglyme,tetraglyme, phosphine, carbonyl, dialkyl sulfide, vinyltrimethylsilane,and allyltrimethylsilane.
 11. The method according to claim 1, whereinthe precursor comprises a composition selected from the group consistingof: Lewis base stabilized Ir(I) 13-ketoiminates of formula II:

wherein R, R′, and R″ are the same or different, and are independentlyselected from the group consisting of H, aryl, perfluoroaryl, C₁-C₆alkyl, or C₁-C₆ perfluoroalkyl, and L is a coordinating Lewis base. 12.The method according to claim 11, wherein the coordinating Lewis base isselected from the group consisting of alkene, diene, cycloalkene,cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetricalor asymmetrical), amine, diamine, triamine, tetraamine, ether,tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine,carbonyl, dialkyl sulfide, vinyltrimethylsilane, andallyltrimethylsilane.
 13. The method according to claim 1, wherein thedecomposition of the precursor and deposition of iridium on thesubstrate is carried out by chemical vapor deposition.
 14. The methodaccording to claim 1, wherein the iridium deposited on the substrate isprocessed to yield an iridium-containing film element on the substrate,having critical dimensional characteristics below about 0.5 micron. 15.The method according to claim 14, wherein the decomposition of theprecursor and deposition of iridium on the substrate is carried out bychemical vapor deposition.
 16. A method of forming a microelectronicdevice or precursor structure on a substrate, including an electrodeoperatively associated with a high-temperature dielectric orferroelectric material deposited thereover, said method comprising: (A)forming an iridium-containing film on the substrate, from aniridium-containing precursor thereof which is decomposable to depositiridium on the substrate, comprising: (i) decomposing the precursor anddepositing iridium on the substrate in an oxidizing ambient environment;and (ii) processing the deposited iridium into an iridium-basedelectrode element; and (B) depositing on the iridium-based electrodeelement a high temperature dielectric and/or ferroelectric material. 17.The method according to claim 16, wherein the iridium-based electrodeelement has deposited thereon a high temperature dielectric material.18. The method according to claim 16, wherein the iridium-basedelectrode element has deposited thereon a high temperature ferroelectricmaterial selected from the group consisting of SBT and PZT.
 19. Themethod according to claim 16, wherein the microelectronic device orprecursor structure comprises a DRAM or FRAM capacitor device orstructure.
 20. The method according to claim 16, wherein the hightemperature dielectric and/or ferroelectric material comprises amaterial selected from the group consisting of SBT, PZT, BST, PLZT,PNZT, and LCMO.
 21. The method according to claim 16, wherein theiridium deposited on the substrate comprises elemental iridium.
 22. Themethod according to claim 16, wherein the iridium deposited on thesubstrate comprises iridium oxide or a combination of iridium andiridium oxide.
 23. The method according to claim 16, wherein theprecursor comprises a composition selected from the group consisting of:Lewis base stabilized Ir(I) β-diketonates of formula I:

wherein R and R′ may be alike or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base; and Lewis base stabilized Ir(I) β-ketoiminatesof formula II:

wherein R, R′, and R″ are the same or different, and are independentlyselected from the group consisting of H, aryl, perfluoroaryl, C₁-C₆alkyl, or C₁-C₆ perfluoroalkyl, and L is a coordinating Lewis base. 24.The method according to claim 23, wherein the coordinating Lewis base isselected from the group consisting of alkene, diene, cycloalkene,cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetricalor asymmetrical), amine, diamine, triamine, tetraamine, ether,tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine,carbonyl, dialkyl sulfide, vinyltrimethylsilane, andallyltrimethylsilane.
 25. The method according to claim 23, wherein theoxidizing ambient environment comprises air.
 26. The method according toclaim 16, wherein steps (A)(i), (A)(ii) and (B) are carried out in thesame oxidizing ambient environment.
 27. A microelectronic devicestructure comprising an iridium oxide electrode element formed in anoxidizing ambient environment and overlaid by a high temperaturedielectric, wherein the electrode is conductively operative in relationto the high temperature dielectric.
 28. The microelectronic devicestructure according to claim 27, wherein the high temperature dielectriccomprises a material selected from the group consisting of SBT, PZT,BST, PLZT, PNZT, and LaCaMnO₃.
 29. The microelectronic device structureaccording to claim 27, wherein the high temperature dielectric comprisesSBT.
 32. (Amended) A composition comprising an organic solvent solutionof an Ir(I) reagent, wherein said Ir(I) reagent is selected from thegroup consisting of: Lewis base stabilized Ir(I) β-diketonates offormula I:

wherein R and R′ may be alike or different and may be H, aryl,perfluoroaryl, C₁-C₆ alkyl, or C₁-C₆ perfluoroalkyl, and L is acoordinating Lewis base; and Lewis base stabilized Ir(I) β-ketoiminatesof formula II:

wherein R, R′, and R″ are the same or different, and are independentlyselected from the group consisting of H, aryl, perfluoroaryl, C₁-C₆alkyl, or C₁-C₆ perfluoroalkyl, and L is a coordinating Lewis base,wherein the coordinating Lewis base is selected from the groupconsisting of alkene, diene, cycloalkene, cyclodiene, cyclooctatetraene,alkyne, substituted alkyne (symmetrical or asymmetrical), amine,diamine, triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme,triglyme, tetraglyme, phosphine, carbonyl, dialkyl sulfide,vinyltrimethylsilane, and allyltrimethylsilane.